JP2019144408A - Coloring resin composition, color filter, and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored resin composition having good electrical reliability, a color filter having pixels formed by using the colored resin composition, and an image display device having the color filter. A colored resin composition containing (A) a colorant, (B) a dispersant, (C) a solvent, (D) a binder resin, (E) a photopolymerizable monomer, and (F) a photopolymerization initiator. The dispersant (B) contains a dispersant having a repeating unit of a specific structure in an amount of 50 mol% or more, and the binder resin (D) contains an alkali-soluble resin having a repeating unit of a specific structure. A characteristic colored resin composition. [Selection diagram] None

Description

  The present invention relates to a colored resin composition, a color filter, and an image display device.

  Conventionally, pigment dispersion methods, dyeing methods, electrodeposition methods, and printing methods are known as methods for producing color filters used in liquid crystal display devices and the like. Above all, from the viewpoint of spectral characteristics, durability, pattern shape, accuracy, etc., the pigment dispersion method having excellent characteristics on average is most widely adopted.

In a color filter having pixels formed by using a pigment dispersion method, miniaturization of pigments is being studied in order to achieve high brightness and high contrast. By making the pigment finer, it is considered that the scattering of light transmitted through the color filter by the pigment particles is reduced, and high brightness and high contrast are achieved.
However, since the refined pigment particles tend to aggregate, there is a problem that the dispersibility and dispersion stability are lowered. It is known that the use of a dispersant is effective as a method for improving the dispersibility of the finely divided pigment.

  For example, Patent Document 1 describes a colored resin composition containing a block copolymer having an amine value of 80 to 150 mgKOH / g. Patent Document 2 describes a colored resin composition containing a block copolymer having an acid value of 1 to 18 mgKOH / g and a glass transition temperature of 30 ° C. or higher. Patent Document 3 describes a colored resin composition containing a block copolymer having an amine value of 35 to 110 mgKOH / g and a glass transition temperature of 30 ° C. or higher.

JP 2009-052010 A JP, 2006-122169, A JP 2016-121203 A

In recent years, color filters are required to have sufficient electrical reliability. When the electrical reliability is low, the components contained in the colored resin composition for forming the color filter enter the liquid crystal layer and move in the liquid crystal layer, so that the voltage applied to the liquid crystal layer is maintained for a certain period. This prevents the image from being held and causes a display defect of the image display device.
When the present inventors examined, it turned out that the electrical reliability requested | required in recent years is inadequate in the colored resin composition described in patent documents 1-3.

  Accordingly, an object of the present invention is to provide a colored resin composition having good electrical reliability, a color filter having pixels formed using the colored resin composition, and an image display device having the color filter.

As a result of intensive studies by the present inventors, it has been found that the above-mentioned problems can be solved by including a specific dispersant and a specific alkali-soluble resin in the colored resin composition, leading to the present invention.
That is, the present invention has the following configurations [1] to [4].

[1] A colored resin composition containing (A) a pigment, (B) a dispersant, (C) a solvent, (D) a binder resin, (E) a photopolymerizable monomer, and (F) a photopolymerization initiator. And
The (B) dispersant includes a dispersant (b) having 50 mol% or more of a repeating unit represented by the following general formula (I):
The colored resin composition, wherein the binder resin (D) includes an alkali-soluble resin (d) having a repeating unit represented by the following general formula (i).

(In formula (I), R ¹ represents a hydrogen atom or a methyl group. R ² represents an alkyl group having 3 or less carbon atoms which may have a substituent.)

(In formula (i), R ^d1 represents a hydrogen atom or a methyl group.
R ^d2 represents a trivalent hydrocarbon group which may have a substituent.
R ^d3 represents a hydrogen atom or a methyl group.
R ^d4 represents a divalent hydrocarbon group which may have a substituent. )

[2] The colored resin composition according to [1], wherein the (A) pigment contains a halogenated zinc phthalocyanine pigment.
[3] A color filter having pixels created using the colored resin composition according to [1] or [2].
[4] An image display device having the color filter according to [3].

  According to the present invention, it is possible to provide a colored resin composition having good electrical reliability, a color filter having pixels formed using the colored resin composition, and an image display device having the color filter.

FIG. 1 is a schematic cross-sectional view showing an example of an organic EL display device having the color filter of the present invention.

The constituent requirements and the like of the present invention will be described in detail below, but these are examples of embodiments of the present invention and are not limited to these contents.
In addition, “(meth) acryl”, “(meth) acrylate” and the like mean “acryl and / or methacryl”, “acrylate and / or methacrylate” and the like, for example, “(meth) acrylic acid” is “ It means “acrylic acid and / or methacrylic acid”. Further, “total solid content” means all components other than the solvent component contained in the pigment dispersion or the colored resin composition.

In the present invention, “weight average molecular weight” refers to polystyrene-reduced weight average molecular weight (Mw) by GPC (gel permeation chromatography).
In the present invention, the “amine value” means an amine value in terms of effective solid content unless otherwise specified, and is a value represented by the mass of KOH equivalent to the base amount per 1 g of the solid content of the dispersant. .
In the present invention, “CI” means a color index.

[1] Constituent Components of Colored Resin Composition Each constituent component of the colored resin composition of the present invention will be described below. The colored resin composition according to the present invention comprises (A) a colorant, (B) a dispersant, (C) a solvent, (D) a binder resin, (E) a photopolymerizable monomer, and (F) a photopolymerization initiator. As an essential component, if necessary, other additives other than the above components may be blended.
Hereinafter, each component will be described.

[1-1] (A) Colorant The colored resin composition of the present invention contains (A) a colorant as an essential component. Examples of the colorant include pigments and dyes. As the pigment, for example, when forming a pixel of a color filter, pigments of various colors such as a red pigment, a blue pigment, a green pigment, a yellow pigment, a purple pigment, an orange pigment, and a brown pigment can be used. Examples of the chemical structure include organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. In addition, various inorganic pigments can be used. Hereinafter, specific examples of usable pigments are indicated by pigment numbers. The following “CI” means a color index (CI).

  Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276, and the like. Among these, from the viewpoint of dispersion stability, C.I. I. Pigment red 177, 254, or 275, and more preferably C.I. I. Pigment Red 177 or 254.

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Among these, from the viewpoint of dispersion stability, C.I. I. Pigment Blue 15: 3 or 15: 6, more preferably C.I. I. Pigment Blue 15: 6.

  Examples of the green pigment include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58 or 59. . Among these, from the viewpoint of dispersion stability, C.I. I. Pigment green 36, 58 or 59, more preferably C.I. I. Pigment Green 58 or 59.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208, and the like. Among these, from the viewpoint of dispersion stability, C.I. I. Pigment Yellow 129, 138, 139, 150 or 185, more preferably C.I. I. Pigment Yellow 138, 150 or 185.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Among these, from the viewpoint of dispersion stability, C.I. I. Pigment violet 23 or 29, more preferably C.I. I. Pigment Violet 23.

  Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 and the like.

  In addition, examples of the inorganic pigment include barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, and chromium oxide.

  Of the various pigments described above, C.I. I. Pigment red 254, C.I. I. Pigment red 177, C.I. I. Pigment blue 15: 6, C.I. I. Pigment green 58, C.I. I. Pigment green 59, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 185 or C.I. I. Pigment Violet 23 is preferred, and C.I. I. Pigment green 58 or C.I. I. More preferred are zinc halide phthalocyanine pigments such as CI Pigment Green 59.

A plurality of the above-mentioned various pigments can be used in combination. For example, in order to adjust the chromaticity, a green pigment and a yellow pigment can be used in combination, a blue pigment and a purple pigment can be used in combination, or a red pigment and a yellow pigment can be used in combination.
These pigments are preferably used after being subjected to a dispersion treatment so that the average particle size is usually 1 μm or less, preferably 0.5 μm or less, more preferably 0.3 μm or less.

  The average primary particle size of these pigments is usually 100 nm or less, preferably 50 nm or less, more preferably 40 nm or less, and particularly preferably 10 nm or more and 30 nm or less. Since the present invention is particularly effective in the case of a composition containing a highly atomized pigment, the case of containing a pigment having an average primary particle size of 10 nm to 30 nm is particularly preferable.

  When forming a light shielding material such as a black matrix of a color filter using the colored resin composition of the present invention, a black pigment can be used. The black pigment may be used alone, or may be used by mixing the above-mentioned pigments such as red, green and blue. Examples of black pigments that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, and titanium black. Among these, carbon black and titanium black are preferable from the viewpoints of light shielding rate and image characteristics.

  Examples of carbon black include, for example, MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32 as products manufactured by Mitsubishi Chemical Corporation. , # 33, # 40, # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B As a product made by Degussa, etc., Printex3, Printex3OP, Printex30 Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Print ex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack 350, SpecialBlack250, SpecialBlack100, SpecialBlack6, Special Black 5, Special Black 4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Col or Black FW18, Color Black FW200, Color Black S160, Color Black S170 etc. are products manufactured by Cabot Corporation, Monarch120, Monarch280, Monch1600, Monch800, Monch1800, Monch1 REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN X 72R, ELFTEX-8, etc. are products made by Birler, such as Raven11, Raven14, Raven15, Raven16, Raven22, Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven10R, Raven10R, Raven10R, Raven10R, Raven10R, Raven10R , RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000 and the like.

  For the production of a resin black matrix having a high optical density and a high surface resistivity, it is particularly preferable to use resin-coated carbon black. The resin-coated carbon black is, for example, disclosed in JP-A-9-26571, JP-A-9-71733, JP-A-9-95625, JP-A-9-238863, or JP-A-11-60989. It can be obtained by treating known carbon black by the method described in the publication.

  Further, titanium black was prepared by heating a mixture of titanium dioxide and titanium metal in a reducing atmosphere for reduction (Japanese Patent Laid-Open No. 49-5432), and by high-temperature hydrolysis of titanium tetrachloride. A method of reducing ultrafine titanium dioxide in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069). And a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and reducing it at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610). It is not limited. Examples of commercially available titanium black include Titanium Black 10S, 12S, 13R, 13M, and 13M-C manufactured by Mitsubishi Materials Corporation.

  As an example of another black pigment, a plurality of pigments such as red, green, and blue can be mixed and used as a black pigment. Color materials that can be mixed for preparing a black pigment include Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170), Safranin OK70: 100 (50240), Erioglaucine X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimla First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. In addition, other pigments that can be used for mixing are C.I. I. For example, C.I. I. Pigment Yellow 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Pigment orange 36, 43, 51, 55, 59, 61, C.I. I. Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Pigment violet 19, 23, 29, 30, 37, 40, 50, C.I. I. Pigment blue 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Pigment green 7, C.I. I. And CI pigment brown 23, 25, 26. The numbers in parentheses above indicate the color index (CI).

  The particle size of these black pigments is preferably in the same range as described above for the pigments other than black.

  On the other hand, as the dye, for example, a dye having xanthene, anthraquinone, or phthalocyanine as a basic skeleton and having a sulfonic acid group and / or a sulfonate group can be used. Specifically, xanthene dyes include Acid Red 52, Acid Red 87, Acid Red 91, Acid Red 92, Acid Red 94, Acid Red 289, and anthraquinone dyes include Acid Red 80, Acid Green 25, and Acid. Examples of the green 27, acid blue 25, acid blue 78, acid blue 112, acid blue 182, acid violet 34, acid violet 43, and phthalocyanine dyes include direct blue 86, direct blue 87, and acid blue 249.

  In the colored resin composition of the present invention, the content ratio of these (A) colorants is not particularly limited, but is generally 1% by mass or more, preferably 5% by mass or more, and more preferably 10% by mass or more in the total solid content. 20% by mass or more is more preferable, 25% by mass or more is more preferable, 30% by mass or more is particularly preferable, and usually 80% by mass or less, 60% by mass or less is preferable, 50% by mass or less is more preferable, 40% by mass. % Or less is more preferable. By setting it to the above lower limit value or more, there is a tendency to achieve desired chromaticity and film thickness as a color filter, and by setting it to the upper limit value or less, dispersion stability tends to be improved.

  Moreover, when (A) the colorant contains a pigment, the content ratio of the pigment is not particularly limited, but is generally 1% by mass or more, preferably 5% by mass or more, and more preferably 10% by mass or more in the total solid content. % By mass or more is more preferred, 25% by mass or more is more preferred, 30% by mass or more is particularly preferred, usually 80% by mass or less, 60% by mass or less is preferred, 50% by mass or less is more preferred, and 40% by mass. The following is more preferable. By setting it as the said lower limit or more, there exists a tendency for it to become the desired chromaticity and film thickness as a color filter, and there exists a tendency for dispersion stability to become favorable by setting it as the said upper limit or less.

[1-2] (B) Dispersant The colored resin composition of the present invention contains (B) a dispersant as an essential component. By including the (B) dispersant, the (A) colorant can be stably dispersed.
The dispersant (B) in the colored resin composition of the present invention is a dispersant (b) having a repeating unit represented by the following general formula (I) of 50 mol% or more (hereinafter abbreviated as “dispersant (b)”). May be included).

In the formula (I), R ¹ represents a hydrogen atom or a methyl group. R ² represents an alkyl group having 3 or less carbon atoms which may have a substituent.

The repeating unit represented by the general formula (I) contained in the dispersant (b) has a low affinity for liquid crystal molecules due to the short carbon number of the alkyl group of R ² . Therefore, the affinity of the colored resin composition itself with the liquid crystal molecules is obtained by including the dispersing agent (b) having 50 mol% or more of the repeating unit represented by the general formula (I) in the colored resin composition. Is considered to be low. Furthermore, the steric repulsion between the dispersant (b) and the colorant is suppressed, and the adsorption of the dispersant (b) to the colorant is promoted, so that the release of the free dispersant into the liquid crystal layer is suppressed. It is considered that the voltage holding ratio is improved. Moreover, it is considered that the short carbon number of R ² is high in heat resistance, is not easily thermally decomposed by heat treatment, and is less likely to cause luminance reduction due to coloring.

(R ² )
In formula (I), R ² represents an alkyl group having 3 or less carbon atoms which may have a substituent.

The alkyl group may be linear or branched, but is preferably linear from the viewpoint of suppressing steric repulsion with the colorant.
Further, the number of carbon atoms of the alkyl group is not particularly limited as long as it is 3 or less, but 2 or less is preferable, and 1 is more preferable. There exists a tendency for electrical reliability to become favorable by setting it as the said upper limit or less. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an iso-propyl group. From the viewpoint of electrical reliability, a methyl group or an ethyl group is preferable, and a methyl group is more preferable.
The substituent that the alkyl group may have is not particularly limited, and examples thereof include a halogen atom and a hydroxyl group, but from the viewpoint of electrical reliability, an unsubstituted group is particularly preferable.

  The dispersant (b) contains the repeating unit represented by the general formula (I), but may further contain other repeating units. Among other repeating units, from the viewpoint of dispersibility, it is preferable to include a repeating unit represented by the following general formula (II).

In formula (II), R ³ represents a hydrogen atom or a methyl group. X represents a divalent linking group. R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. R ⁴ and R ⁵ may be bonded to each other to form a cyclic structure.

(X)
In formula (II), X represents a divalent linking group.
Examples of the divalent linking group include a single bond, an alkylene group, an arylene group, and an alkyloxyalkyl group. Among these, an alkylene group is preferable from the viewpoint of dispersibility.

The alkylene group may be linear, branched or cyclic, but is preferably linear from the viewpoint of dispersibility.
The number of carbon atoms of the alkylene group is usually preferably 1 or more and 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the amount is not less than the lower limit, the dispersion stability tends to be improved, and when the amount is not more than the upper limit, the developability and the storage stability tend to be improved.
Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, and an octylene group. From the viewpoint of dispersibility, a methylene group or an ethylene group is preferable. Groups are more preferred.

(R ⁴ and R ⁵⁾
In formula (II), R ⁴ and R ⁵ each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. And R ⁴ and R ⁵ may be bonded to each other to form a cyclic structure.

The alkyl group may be linear, branched, cyclic, or a combination thereof, but is preferably linear from the viewpoint of dispersibility.
Although carbon number of an alkyl group is not specifically limited, From a dispersible viewpoint, it is 1 or more normally, 10 or less are preferable, 6 or less are more preferable, 4 or less are more preferable, 3 or less are more preferable, 2 or less The following are particularly preferred:

  Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, a cyclohexylmethyl group, and an octyl group. To methyl group, ethyl group, propyl group, butyl group, pentyl group, or hexyl group, more preferably methyl group, ethyl group, propyl group, or butyl group, methyl group or ethyl group More preferably.

The aryl group may be a monovalent aromatic hydrocarbon ring group or a monovalent aromatic heterocyclic group.
Although carbon number of an aryl group is not specifically limited, From a dispersible viewpoint, it is 6 or more normally, 16 or less are preferable, 12 or less are more preferable, 10 or less are more preferable, and 8 or less are especially preferable.
Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group. Among these, a phenyl group, a methylphenyl group, and an ethylphenyl group , A dimethylphenyl group, or a diethylphenyl group, and more preferably a phenyl group, a methylphenyl group, or an ethylphenyl group.

An aralkyl group is a group in which an alkylene group and an aryl group are bonded. The alkylene group may be linear, branched, cyclic, or a combination thereof. The aryl group may be a monovalent aromatic hydrocarbon ring group or a monovalent aromatic heterocyclic group.
The number of carbon atoms of the aralkyl group is not particularly limited, but from the viewpoint of dispersibility, it is usually 7 or more, preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less. 8 or less is particularly preferable.
Specific examples of the aralkyl group include a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group. Among these, a phenylmethyl group and a phenylethyl group Group, a phenylpropyl group, or a phenylbutyl group is preferable, and a phenylmethyl group or a phenylethyl group is more preferable.

  Examples of the substituent which the alkyl group, aralkyl group or aryl group may have include a halogen atom, an alkoxy group, a benzoyl group and a hydroxyl group.

Among these, dispersibility, storage stability, electrical reliability, from the viewpoint of developability, it is preferable that R ⁴ and R ⁵ are each independently an alkyl group, or an aralkyl group, specifically, R ⁴ and More preferably, R ⁵ is a methyl group.

In the formula (II), examples of the cyclic structure formed by combining R ⁴ and R ⁵ with each other include, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocycle or a condensed ring formed by condensing two of these. Is mentioned. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specific examples include the following.

  These cyclic structures may further have a substituent.

  On the other hand, among other repeating units, it is preferable to include a repeating unit represented by the following general formula (III) from the viewpoint of dispersion stability.

In formula (III), R ⁶ represents a hydrogen atom or a methyl group. Z represents a divalent linking group. R ^{7 to} R ⁹ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. 2 or more of R ^{7 to} R ⁹ may be bonded to each other to form a cyclic structure. A ⁻ represents a counter anion.

Moreover, as Z in the formula (III), those exemplified as X in the formula (II) can be preferably employed. As the alkyl group which may have a substituent in R ^{7 to} R ^9, the aryl group which may have a substituent, and the aralkyl group which may have a substituent, the above formula (II) Preferably used are the alkyl groups optionally having substituents in R ⁴ and R ⁵ , aryl groups optionally having substituents, and aralkyl groups optionally having substituents. can do.

(A ^-)
In formula (III), A ⁻ represents a counter anion. Examples of the counter anion include Cl ⁻ , Br ⁻ , I ⁻ , ClO ⁴⁻ , BF ⁴⁻ , CH ₃ COO ⁻ , and PF ₆ ⁻ .

In the formula (III), examples of the cyclic structure formed by bonding two or more of R ^{7 to} R ⁹ to each other include, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocyclic ring or two condensed thereof The condensed ring formed is mentioned. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specific examples include the following.

In said formula, R is either R < ⁷ > -R < ⁹ >. Moreover, these cyclic structures may further have a substituent.

  Moreover, among other repeating units, it is preferable that the repeating unit represented by the following general formula (IV) is included from a viewpoint of dispersibility and developability.

In formula (IV), R ¹⁰ represents a hydrogen atom or a methyl group. R ¹¹ represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.

(R ¹¹ )
In formula (IV), R ¹¹ represents a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or an aralkyl group that may have a substituent. Represent.

The alkyl group may be linear, branched, cyclic, or a combination thereof, but is preferably linear from the viewpoint of dispersibility.
The number of carbon atoms of the alkyl group is not particularly limited, but from the viewpoint of developability, 4 or more is preferable, 10 or less is preferable, 8 or less is more preferable, and 6 or less is more preferable.

  Specific examples of the alkyl group include a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, a cyclohexylmethyl group, and an octyl group. Among these, from the viewpoint of dispersibility and developability, a butyl group, a pentyl group Group or hexyl group is preferable, and butyl group is more preferable.

The aryl group may be a monovalent aromatic hydrocarbon ring group or a monovalent aromatic heterocyclic group.
Although carbon number of an aryl group is not specifically limited, From a developable viewpoint, it is 6 or more normally, 16 or less are preferable, 12 or less are more preferable, 10 or less are more preferable, and 8 or less are especially preferable.
Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group. Among these, a phenyl group, a methylphenyl group, and an ethylphenyl group , A dimethylphenyl group, or a diethylphenyl group, and more preferably a phenyl group, a methylphenyl group, or an ethylphenyl group.

An aralkyl group is a group in which an alkylene group and an aryl group are bonded. The alkylene group may be linear, branched, cyclic, or a combination thereof. The aryl group may be a monovalent aromatic hydrocarbon ring group or a monovalent aromatic heterocyclic group.
The number of carbon atoms of the aralkyl group is not particularly limited, but from the viewpoint of developability, it is usually 7 or more, preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less. 8 or less is particularly preferable.
Specific examples of the aralkyl group include a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group. Among these, a phenylmethyl group and a phenylethyl group Group, a phenylpropyl group, or a phenylbutyl group is preferable, and a phenylmethyl group or a phenylethyl group is more preferable.

  Examples of the substituent which the alkyl group, aralkyl group or aryl group may have include a halogen atom, an alkoxy group, a benzoyl group and a hydroxyl group.

Among these, from the viewpoint of developability, R ¹¹ is preferably an alkyl group, and more preferably a butyl group.

  In the dispersant (b), the content of the repeating unit represented by the general formula (I) is 50 mol% or more, preferably 55 mol% or more, more preferably 60 mol% or more, and 65 mol% or more. Is more preferable, 70 mol% or more is particularly preferable, 95 mol% or less is preferable, 90 mol% or less is more preferable, and 80 mol% or less is more preferable. There exists a tendency for electrical reliability to become favorable by setting it as the said lower limit or more, and there exists a tendency for dispersibility to improve by setting it as the said upper limit or less.

  When the dispersant (b) contains the repeating unit represented by the general formula (II), the content ratio is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, and more preferably 10 mol% or more. Is more preferable, 15 mol% or more is particularly preferable, 45 mol% or less is preferable, 40 mol% or less is more preferable, 35 mol% or less is further preferable, and 30 mol% or less is particularly preferable. Dispersion stability tends to be improved by setting it to the lower limit or higher, and storage stability, electrical reliability, and developability tend to be improved by setting the upper limit or lower.

  When the dispersant (b) contains the repeating unit represented by the general formula (III), the content ratio is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, and more preferably 10 mol% or more. Is more preferable, 15 mol% or more is particularly preferable, 100 mol% or less is preferable, 45 mol% or less is more preferable, 40 mol% or less is more preferable, and 35 mol% or less is particularly preferable. Dispersion stability tends to be improved by setting it to the lower limit value or more, and electrical reliability and developability tend to be improved by setting the upper limit value or less.

  When the dispersant (b) contains the repeating unit represented by the general formula (IV), the content ratio is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, and 8 mol% or more. Is more preferably 10 mol% or more, more preferably 30 mol% or less, more preferably 25 mol% or less, further preferably 20 mol% or less, and particularly preferably 15 mol% or less. When the amount is not less than the lower limit, the dispersion stability tends to be improved, and when the amount is not more than the upper limit, the developability tends to be improved.

  The dispersant (b) is not particularly limited as long as it has the repeating unit represented by the general formula (I), but is represented by the general formula (I) from the viewpoint of further improving dispersibility. A block copolymer containing a B block having a repeating unit and an A block having another repeating unit is preferred. The block copolymer is preferably an AB block copolymer or a BAB block copolymer. From the viewpoint of dispersibility, the A block preferably contains a repeating unit represented by the general formula (II) and / or a repeating unit represented by the general formula (III). It is more preferable that the repeating unit represented by this is included. In addition, from the viewpoint of heat resistance, the B block contains the repeating unit represented by the general formula (I), the repeating unit represented by the general formula (I), and the general formula (IV). It is preferred that the repeating unit represented is included.

  The acid value of the dispersant (b) is preferably lower from the viewpoint of dispersibility, and particularly preferably 0 mgKOH / g. Here, the acid value represents the number of mg of KOH necessary for neutralizing 1 g of the solid content of the dispersant.

  On the other hand, the amine value of the dispersant (b) is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, still more preferably 60 mgKOH / g or more, and even more preferably 80 mgKOH / g or more, 100 mgKOH / g or more is particularly preferable, 170 mgKOH / g or less is preferable, 150 mgKOH / g or less is more preferable, 140 mgKOH / g or less is more preferable, and 130 mgKOH / g or less is preferable. Particularly preferred. Dispersibility tends to be improved by setting it to the lower limit value or more, and developability tends to be improved by setting the upper limit value or less. Here, the amine value represents an amine value in terms of effective solid content, and is a value represented by the mass of KOH equivalent to the amount of base per 1 g of the solid content of the dispersant.

  Further, the molecular weight of the dispersant (b) is not particularly limited, but is preferably 1,000 or more, more preferably 4,000 or more in terms of polystyrene-equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography). 6,000 or more is more preferable, 30,000 or less is preferable, 20,000 or less is more preferable, and 10,000 or less is more preferable. When the amount is not less than the lower limit, the dispersion stability tends to be good, and when the amount is not more than the upper limit, there is a tendency that a decrease in developability can be suppressed.

  The dispersant (b) can be produced by a known method, but when it is a block copolymer, it can be produced, for example, by subjecting the monomer for introducing each repeating unit to living polymerization. . Examples of the living polymerization method include JP-A-9-62002, JP-A-2002-31713, and P.I. Lutz, P.M. Masson et al, Polym. Bull. 12, 79 (1984), B.R. C. Anderson, G.M. D. Andrews et al, Macromolecules, 14, 1601 (1981), K. et al. Hatada, K .; Ute, et al, Polym. J. et al. 17, 977 (1985), 18, 1037 (1986), Koichi right hand, Koichi Hatada, polymer processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Thesis, 46, 189 (1989), M.M. Kuroki, T .; Aida, J .; Am. Chem. Soc, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D.C. Y. Sogoh, W .; R. Known methods described in Hertler et al, Macromolecules, 20, 1473 (1987) and the like can be employed.

  In the present invention, other dispersant can be used in combination with the dispersant (b). Examples of other dispersants include Disperbyk (registered trademark, the same shall apply hereinafter) -161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182, Disperbyk-2000, Disperbyk-2001, Disperbyk-2001, Disperbyk-2001. -LPN6919, BYK-LPN21116 (above, manufactured by BYK (BYK)), Solsperse (registered trademark, the same shall apply hereinafter) 24000, Solsperse 76500 (manufactured by Lubrizol Co., Ltd.), Azisper (registered trademark, same shall apply hereinafter) PB821 And commercial products such as Ajisper PB822, Azisper PB823, Azisper PB824, Azisper PB827 (Ajinomoto Fine Techno Co., Ltd.).

  In the colored resin composition of the present invention, the content ratio of the (B) dispersant is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, based on the total solid content of the colored resin composition. 4% by mass or more is more preferable, 5% by mass or more is particularly preferable, 20% by mass or less is preferable, 15% by mass or less is more preferable, 12% by mass or less is further preferable, and 10% by mass or less is particularly preferable. Dispersibility tends to be good when it is at least the lower limit, and reliability tends to improve when it is at most the upper limit.

  In the colored resin composition of the present invention, the content ratio of the dispersant (b) is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more based on the total solid content of the colored resin composition. Preferably, 2% by mass or more is more preferable, 3% by mass or more is particularly preferable, 15% by mass or less is preferable, 12% by mass or less is more preferable, 10% by mass or less is further preferable, and 8% by mass or less is particularly preferable. . When it is at least the lower limit, the heat resistance tends to be improved, and when it is at most the upper limit, the reliability tends to be improved.

  Although the content rate of the dispersing agent (b) in the dispersing agent (B) of the colored resin composition of the present invention is not particularly limited, it is preferably 10% by mass or more, more preferably 30% by mass or more, and further preferably 40% by mass or more. 50 mass% or more is particularly preferable, 100 mass% or less is preferable, 95 mass% or less is more preferable, 90 mass% or less is further preferable, and 85 mass% or less is particularly preferable. When it is at least the lower limit value, the reliability tends to be improved, and when it is at most the upper limit value, the dispersibility tends to be improved.

[1-3] (C) Solvent (C) The solvent dissolves or disperses the colorant, dispersant, binder resin, photopolymerizable monomer, photopolymerization initiator, and other components in the colored resin composition of the present invention. And has a function of adjusting the viscosity.
The solvent (C) may be any solvent that can dissolve or disperse each component.

  Examples of such solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, Propylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl -3-Methoxybutanol Triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, glycol monoalkyl ethers such as tripropylene glycol methyl ether;

Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol Roh ether acetate, triethylene glycol monoethyl ether acetate, glycol alkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;

Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;
Ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Like acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone Ketones;
Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Examples thereof include nitriles such as acetonitrile and benzonitrile.

  Commercially available solvents corresponding to the above include mineral spirit, Barsol # 2, Apco # 18 Solvent, Apco thinner, Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names) and the like. These solvents may be used alone or in combination of two or more.

When forming pixels of a color filter by photolithography, a solvent having a boiling point in the range of 100 to 200 ° C. (under a pressure of 101.25 [hPa], hereinafter the same applies to the boiling point) is selected. Is preferred. More preferably, it has a boiling point of 120-170 ° C.
Glycol alkyl ether acetates are preferred from the viewpoints of good balance between the solvent, applicability, surface tension, etc., and relatively high solubility of the components in the composition.

  In addition, glycol alkyl ether acetates may be used alone or in combination with other solvents. As the solvent used in combination, glycol monoalkyl ethers are particularly preferable. Of these, propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituent components in the composition. Glycol monoalkyl ethers are highly polar, and if the amount added is too large, the pigment tends to aggregate, and the storage stability such as the viscosity of the colored resin composition obtained later tends to decrease. The proportion of glycol monoalkyl ethers in the solvent is preferably 5% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass.

It is also preferable to use a solvent having a boiling point of 150 ° C. or higher in combination. By using such a high boiling point solvent in combination, the colored resin composition becomes difficult to dry, but it has the effect of making it difficult for the pigment dispersion liquid to break down due to rapid drying. The content of the high-boiling solvent is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass with respect to the solvent (B). By setting it to the above lower limit value or more, for example, there is a tendency to easily prevent a color material component from being precipitated and solidified at the tip of the slit nozzle to cause a foreign matter defect, and by setting it to the upper limit value or less, There is a tendency that it is easy to avoid a problem that the drying speed becomes slow and causes problems such as tact defects in the vacuum drying process and pin marks of prebaking.
The solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a solvent having a boiling point of 150 ° C. or higher may not be separately contained.
Preferred examples of the high boiling point solvent include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diester. Examples include acetate and triacetin.

When forming a pixel of a color filter by the ink jet method, a solvent having a boiling point of usually 130 ° C. or higher and 300 ° C. or lower, preferably 150 ° C. or higher and 280 ° C. or lower is appropriate. By setting it as the said lower limit or more, there exists a tendency for the uniformity of the coating film obtained to become favorable, and there exists a tendency for the residual solvent at the time of baking to be easy to reduce by setting it as the said upper limit or less.
The solvent vapor pressure is usually 10 mmHg or less, preferably 5 mmHg or less, more preferably 1 mmHg or less, from the viewpoint of the uniformity of the resulting coating film.

  In addition, in the production of color filters by the ink jet method, the ink emitted from the nozzle is very fine, from several to several tens of pL, so the solvent evaporates and concentrates before landing on the periphery of the nozzle opening or in the pixel bank.・ Tends to dry. In order to avoid this, it is preferable that the solvent has a high boiling point. Specifically, it is preferable to include a solvent having a boiling point of 180 ° C. or higher. More preferably, it contains a solvent having a boiling point of 200 ° C. or higher, particularly preferably a boiling point of 220 ° C. or higher. The high boiling point solvent having a boiling point of 180 ° C. or higher is preferably 50% by mass or more, more preferably 70% by mass or more, and most preferably 90% by mass or more in the total solvent contained in the colored resin composition. By setting it to the lower limit value or more, there is a tendency that the effect of preventing evaporation of the solvent from the droplets is sufficiently exhibited.

Preferred examples of the high boiling point solvent include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diester. Examples include acetate and triacetin.
Furthermore, it is also effective to partially contain a solvent having a boiling point lower than 180 ° C. in order to adjust the viscosity of the colored resin composition and the solubility of the solid content. As such a solvent, a solvent having low viscosity, high solubility, and low surface tension is preferable, and ethers, esters, ketones, and the like are preferable. Of these, cyclohexanone, dipropylene glycol dimethyl ether, cyclohexanol acetate, and the like are particularly preferable.

  On the other hand, when the solvent contains alcohols, the ejection stability in the ink jet method may deteriorate. Therefore, it is preferable that alcohol is 20 mass% or less in all the solvents, 10 mass% or less is more preferable, and 5 mass% or less is especially preferable.

  Although the content rate of the solvent which occupies for the colored resin composition of this invention is not specifically limited, Usually, it is 99 mass% or less, Preferably it is 90 mass% or less, More preferably, it is 85 mass% or less. There exists a tendency which becomes easy to form a coating film by setting it as the said upper limit or less. On the other hand, the lower limit of the solvent content is usually 70% by mass or more, preferably 75% by mass or more, and more preferably 80% by mass or more in consideration of viscosity suitable for application.

[1-4] (D) Binder resin The colored resin composition of the present invention contains (D) a binder resin. (D) By containing a binder resin, film curability by photopolymerization and solubility by a developer can be compatible.
The binder resin (D) in the colored resin composition of the present invention may be referred to as an alkali-soluble resin (d) having a repeating unit represented by the following general formula (i) (hereinafter referred to as “alkali-soluble resin (d)”). Yes.)

In formula (i), R ^d1 represents a hydrogen atom or a methyl group.
R ^d2 represents a trivalent hydrocarbon group which may have a substituent.
R ^d3 represents a hydrogen atom or a methyl group.
R ^d4 represents a divalent hydrocarbon group which may have a substituent.

  The colored resin composition of the present invention contains the alkali-soluble resin (d), but the carboxyl group in the repeating unit represented by the general formula (i) is sufficiently separated from the main chain. Since the carboxyl group is bonded to a highly fluid side chain in this way, intramolecular association due to hydrogen bonding between the carboxyl groups is unlikely to occur, and the ethylenic double bond can be easily directed to the outside of the molecule to cure. It is considered that the voltage holding ratio increases. Further, it is considered that the contact efficiency between the carboxyl group and the developer is high, the dissolution time is shortened, and a pattern having good linearity is easily obtained.

(R ^d2 )
In formula (i), R ^d2 represents a trivalent hydrocarbon group which may have a substituent. Examples of the trivalent hydrocarbon include a trivalent aliphatic hydrocarbon group.
Examples of the trivalent aliphatic hydrocarbon group include linear, branched, cyclic, and combinations thereof.
The number of carbon atoms of the trivalent aliphatic hydrocarbon group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 15 or less, preferably 10 or less, and more preferably 8 or less. More preferred are: When the amount is not less than the lower limit, the solvent affinity tends to be improved, and when the amount is not more than the upper limit, the developability tends to be improved.
Specific examples of the trivalent aliphatic hydrocarbon group include the following.

  Examples of the substituent that the trivalent hydrocarbon group may have include a hydroxy group, a carboxy group, an amino group, a nitro group, and a sulfo group.

(R ^d4 )
In formula (i), R ^d4 represents a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon include a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon ring group.
Examples of the divalent aliphatic hydrocarbon group include linear, branched, cyclic, and combinations thereof.
The number of carbon atoms of the divalent aliphatic hydrocarbon group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, particularly preferably 4 or more, and usually 15 or less, preferably 10 or less, 8 The following is more preferable, and 5 or less is more preferable. There exists a tendency for developability to improve by making it into the said lower limit or more, and there exists a tendency for linearity to improve by making it into the said upper limit or less.
Specific examples of the divalent aliphatic hydrocarbon group include an ethylene group, a propylene group, an isopropylene group, an n-butylene group, a tert-butylene group, and a cyclohexenediyl group. Among these, a cyclohexenediyl group is preferable from the viewpoint of developability.

  On the other hand, in the divalent aromatic hydrocarbon ring group, the number of carbon atoms is not particularly limited, but is usually 6 or more, preferably 7 or more, more preferably 8 or more, more preferably 30 or less, and 20 or less. More preferred is 15 or less. There exists a tendency for developability to improve by making it into the said lower limit or more, and there exists a tendency for linearity to improve by making it into the said upper limit or less.

  The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. As the aromatic hydrocarbon ring group, for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring having two free valences, Examples include acenaphthene ring, fluoranthene ring, fluorene ring and the like.

  Examples of the substituent that the divalent hydrocarbon group may have include a hydroxy group, a carboxy group, an amino group, a nitro group, and a sulfo group.

The alkali-soluble resin (d) has a repeating unit represented by the general formula (i), but may further contain another repeating unit.
Other repeating units are preferably repeating units represented by the following general formula (ii) from the viewpoints of curability and reliability.

In formula (ii), R ^d5 represents a hydrogen atom or a methyl group.
R ^d6 represents a trivalent hydrocarbon group which may have a substituent.
R ^d7 represents a hydrogen atom or a methyl group.

As the trivalent hydrocarbon group which may have a substituent in R ^d6 , those ^exemplified for R ^d2 can be preferably used.

  Moreover, as another repeating unit, the repeating unit represented by the following general formula (iii) from a linear viewpoint is preferable.

In formula (iii), R ^d8 represents a hydrogen atom or a methyl group.
R ^d9 represents a hydrogen atom or a monovalent hydrocarbon group which may have a substituent.

(R ^d9 )
In formula (iii), R ^d9 represents a hydrogen atom or a monovalent hydrocarbon group which may have a substituent.
Examples of the monovalent hydrocarbon group include a monovalent aliphatic hydrocarbon group and a monovalent aromatic hydrocarbon ring group.

Examples of the monovalent aliphatic hydrocarbon group include linear, branched, cyclic, and combinations thereof.
The number of carbon atoms of the monovalent aliphatic hydrocarbon group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, further preferably 5 or more, particularly preferably 7 or more, usually 20 or less, 18 or less. Is preferable, 15 or less is more preferable, and 12 or less is more preferable. When it is at least the lower limit, the linearity tends to be improved, and when it is at most the upper limit, the development solubility tends to be improved.
Specific examples of the monovalent aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a hexyl group, an isohexyl group, and a cyclohexyl group. , A benzyl group, a tricyclodecanyl group, and the like. Among these, a tricyclodecanyl group is preferable from the viewpoint of linearity.

  In the monovalent aromatic hydrocarbon group, the number of carbon atoms is not particularly limited, but it is usually 6 or more, preferably 7 or more, more preferably 8 or more, and preferably 30 or less, more preferably 20 or less, 15 The following is more preferable. There exists a tendency for linearity to improve by making it into the said lower limit or more, and there exists a tendency for solubility to improve by making it into the said upper limit or less.

  The aromatic hydrocarbon ring in the monovalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. As the aromatic hydrocarbon ring group, for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring having one free valence, Examples include acenaphthene ring, fluoranthene ring, fluorene ring and the like.

  Examples of the substituent that the monovalent hydrocarbon group may have include a hydroxy group, a carboxy group, an amino group, a nitro group, and a sulfo group.

  Moreover, as another repeating unit, the repeating unit represented by the following general formula (iv) is preferable from a viewpoint of control of dissolution time.

In formula (iv), R ^d10 represents a hydrogen atom or a methyl group.

  Although the content rate of the repeating unit represented by the said general formula (i) contained in alkali-soluble resin (d) is not specifically limited, 10 mol% or more is preferable, 20 mol% or more is more preferable, 30 mol% or more Is more preferable, 35 mol% or more is particularly preferable, 90 mol% or less is preferable, 70 mol% or less is more preferable, 50 mol% or less is further preferable, and 45 mol% or less is particularly preferable. When it is at least the lower limit, curability and solubility tend to be improved, and when it is at most the upper limit, linearity tends to be improved.

  When the alkali-soluble resin (d) contains the repeating unit represented by the general formula (ii), the content ratio is not particularly limited, but is preferably 0.1 mol% or more, more preferably 1 mol% or more, 5 More preferably, mol% or more, more preferably 10 mol% or more, even more preferably 15 mol% or more, more preferably 90 mol% or less, more preferably 70 mol% or less, further preferably 50 mol% or less, 30 A mol% or less is particularly preferred. When it is at least the lower limit, curability tends to be improved, and when it is at most the upper limit, linearity and solubility tend to be improved.

  When the alkali-soluble resin (d) contains the repeating unit represented by the general formula (iii), the content is not particularly limited, but is preferably 0.1 mol% or more, more preferably 1 mol% or more, and 5 More preferably, mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, more preferably 70 mol% or less, more preferably 60 mol% or less, further preferably 50 mol% or less, A mol% or less is particularly preferred. There exists a tendency for linearity to improve by making it into the said lower limit or more, and there exists a tendency for solubility to improve by making it into the said upper limit or less.

  When the alkali-soluble resin (d) includes a partial structure represented by the general formula (iv), the content ratio is not particularly limited, but is preferably 0.01 mol% or more, more preferably 0.1 mol% or more. 1 mol% or more is further preferable, 5 mol% or more is particularly preferable, 30 mol% or less is preferable, 25 mol% or less is more preferable, 20 mol% or less is further preferable, and 15 mol% or less is particularly preferable. There exists a tendency for linearity to improve by making it into the said lower limit or more, and there exists a tendency for solubility to improve by making it into the said upper limit or less.

  Although the manufacturing method of alkali-soluble resin (d) is not specifically limited, For example, with respect to the copolymer of an epoxy group containing (meth) acrylate and another radical polymerizable monomer, the epoxy group which this copolymer has It is obtained by adding an unsaturated monobasic acid to at least a part of and adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction. In detail, the manufacturing method described in Unexamined-Japanese-Patent No. 2009-036552 is employable.

The (D) binder resin in the colored resin composition of the present invention contains an alkali-soluble resin (d), but may further contain another binder resin (d ′).
The other binder resin (d ′) is not particularly limited as long as it exhibits a function as a binder resin, and is described in International Publication No. 2016/158668 [1-6. -2] linear alkali-soluble resin containing a carboxyl group in the main chain, [1-6-3] a resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the carboxyl group-containing resin, [1 -6-4] (meth) acrylic resin, [1-6-5] epoxy (meth) acrylate resin having a carboxyl group, and the like.

  In the colored resin composition of the present invention, the content ratio of the (D) binder resin is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, based on the total solid content of the colored resin composition. 10% by mass or more is more preferable, 15% by mass or more is more preferable, 20% by mass or more is particularly preferable, 25% by mass or more is most preferable, 40% by mass or less is preferable, and 35% by mass or less is more preferable. 30 mass% or less is more preferable. There exists a tendency for solubility to improve by making it into the said lower limit or more, and there exists a tendency for linearity to improve by making it into the said upper limit or less.

  In the colored resin composition of the present invention, the content ratio of the alkali-soluble resin (d) is not particularly limited, but is preferably 1% by mass or more and more preferably 5% by mass or more with respect to the total solid content of the colored resin composition. 10% by mass or more is more preferable, 12% by mass or more is more preferable, 14% by mass or more is particularly preferable, 40% by mass or less is preferable, 35% by mass or less is more preferable, and 30% by mass or less is more preferable. 25 mass% or less is still more preferable, and 20 mass% or less is especially preferable. There exists a tendency for solubility to improve by making it into the said lower limit or more, and there exists a tendency for linearity to improve by making it into the said upper limit or less.

  Further, the content of the alkali-soluble resin (d) in the binder resin (D) of the colored resin composition of the present invention is not particularly limited, but is preferably 1% by mass or more, more preferably 10% by mass or more, and more preferably 30% by mass or more. Is more preferable, 40 mass% or more is still more preferable, 50 mass% or more is especially preferable, and it is 100 mass% or less normally. There exists a tendency for linearity to improve by setting it as the said lower limit or more.

[1-5] (E) Photopolymerizable monomer The colored resin composition of the present invention contains (E) a photopolymerizable monomer. By containing a photopolymerizable monomer, a strong film by photopolymerization tends to be obtained.
The photopolymerizable monomer is not particularly limited as long as it is a polymerizable low molecular compound, but is preferably an addition polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic compound”). The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and cures by the action of a photopolymerization initiator when the colored resin composition of the present invention is irradiated with actinic rays. In addition, the monomer in this invention means the concept which opposes what is called a polymeric substance, and means the concept also containing a dimer, a trimer, and an oligomer other than the monomer of a narrow sense.
In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenic double bonds in one molecule. The number of ethylenic double bonds of the polyfunctional ethylenic monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably It is 8 or less, more preferably 7 or less. There exists a tendency for it to become high sensitivity by setting it as the said lower limit or more, and there exists a tendency for the solubility to a solvent to improve by setting it as the said upper limit or less.

  Examples of the ethylenic compound include an unsaturated carboxylic acid, an ester thereof with a monohydroxy compound, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, An ester, a polyisocyanate compound and a (meth) acryloyl-containing hydroxy compound obtained by an esterification reaction with a saturated carboxylic acid and a polyvalent carboxylic acid and the polyvalent hydroxy compound such as the above-mentioned aliphatic polyhydroxy compound or aromatic polyhydroxy compound; And an ethylenic compound having a urethane skeleton obtained by reacting.

  Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylol propane triacrylate, trimethylol ethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate. And acrylic esters such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate. In addition, the acrylic acid part of these acrylates is a methacrylic acid ester replaced with a methacrylic acid part, an itaconic acid ester replaced with an itaconic acid part, a crotonic acid ester replaced with a crotonic acid part, or a maleic acid replaced with a maleic acid part Examples include esters.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate, and the like.
The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance but may be a mixture. Typical examples include, for example, condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, adipic acid, butanediol. And condensates of glycerin and the like.

  Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; cyclohexane diisocyanate and isophorone diisocyanate. Alicyclic diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloyloxymethyl) propane, 3- (Meth) acryloyl group-containing hydroxy compounds such as hydroxy (1,1,1-trimethacryloyloxymethyl) propane Reaction products thereof.

In addition, as the ethylenic compound used in the present invention, for example, acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate are also useful.
The ethylenic compound may be a monomer having an acid value. The monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group. The polyfunctional monomer provided is preferred, and particularly preferably in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.

These monomers may be used alone, but since it is difficult to use a single compound in production, two or more kinds may be used in combination. Moreover, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. There is a tendency that the development and dissolution characteristics can be made favorable by setting it to the lower limit value or more, and the production and handling become good by making the upper limit value or less the photopolymerization performance, the surface smoothness of the pixel, etc. There is a tendency to improve the curability. Accordingly, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted so as to fall within the above range. Is preferred.

  In the present invention, more preferred polyfunctional monomers having an acid group are mainly dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinic acid ester of dipentaerythritol pentaacrylate which are commercially available as TO1382 manufactured by Toagosei Co., Ltd. It is a mixture as a component. Other polyfunctional monomers can be used in combination with this polyfunctional monomer. Also, those described in paragraphs [0056] and [0057] of JP2013-140346A can be used.

  Moreover, in this invention, it is preferable to use the polymerizable monomer of Unexamined-Japanese-Patent No. 2013-195971 from a viewpoint of making the chemical resistance of a pixel and the linearity of the edge of a pixel favorable. From the viewpoint of achieving both sensitivity of the coating film and shortening of the development time, it is preferable to use a polymerizable monomer described in JP2013-195974A.

  The content of the photopolymerizable monomer in the colored resin composition of the present invention is not particularly limited, but is generally 0% by mass or more, preferably 5% by mass or more, more preferably in the total solid content of the colored resin composition of the present invention. Is 10% by mass or more, more preferably 15% by mass or more, particularly preferably 20% by mass or more, and usually 80% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, and further preferably 40% by mass. % Or less, particularly preferably 30% by mass or less. Moreover, the ratio with respect to 100 mass parts of (A) coloring agent is 0 mass parts or more normally, Preferably it is 5 mass parts or more, More preferably, it is 10 mass parts or more, More preferably, it is 20 mass parts or more, More preferably, it is 40 mass parts Above, especially preferably 60 parts by mass or more, usually 200 parts by mass or less, preferably 100 parts by mass or less, more preferably 80 parts by mass or less. There exists a tendency for sclerosis | hardenability to improve by setting it as the said lower limit or more, and there exists a tendency for solubility to improve by setting it as the said upper limit or less.

[1-6] (F) Photopolymerization initiator The colored resin composition of the present invention contains (F) a photopolymerization initiator. (F) By containing a photopolymerization initiator, film curability by photopolymerization can be obtained.
(F) The photopolymerization initiator can also be used as a mixture (photopolymerization initiation system) with an accelerator (chain transfer agent) and an additive such as a sensitizing dye added as necessary. The photopolymerization initiation system is a component that has a function of directly absorbing light or photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical.

Examples of the photopolymerization initiator include metallocene compounds including titanocene compounds described in JP-A Nos. 59-152396 and 61-151197, and hexaarylbiimidazoles described in JP-A-10-39503. Derivatives, halomethyl-s-triazine derivatives, radical activators such as N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α- Examples thereof include aminoalkylphenone compounds and oxime ester initiators described in JP-A No. 2000-80068.

Specific examples of the photopolymerization initiator that can be used in the present invention are listed below.
2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 Halomethylated triazine derivatives such as -ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine;

2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′-benzofuryl) vinyl] -1,3,4-oxa Diazole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5 monofuryl-1,3 Halomethylated oxadiazole derivatives such as 4-oxadiazole;
2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole dimer, 2- ( 2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) -4,5-diphenylimidazole dimer, (4'-methoxyphenyl) -4,5- Imidazole derivatives such as diphenylimidazole dimer;
Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether;
Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone;

Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone;
2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p -Isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 1,1,1 An acetophenone derivative such as trichloromethyl- (p-butylphenyl) ketone;
Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone;

benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl P-diethylaminobenzoate;
Acridine derivatives such as 9-phenylacridine, 9- (p-methoxyphenyl) acridine;
Phenazine derivatives such as 9,10-dimethylbenzphenazine;
Anthrone derivatives such as benzanthrone;
Dicyclopentadienyl-Ti-dichloride, dicyclopentagenyl-Ti-bis-phenyl, dicyclopentaenyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, Dicyclopentagenenyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentaenyl-Ti-bis-2,4,6-trifluorophen-1-yl, Dicyclopentagenyl-Ti-2,6-diplorophen-1-yl, dicyclopentagenenyl-Ti-2,4-difluorophen-1-yl, dimethylcyclopentaenyl-Ti-bis-2,3 , 4,5,6-pentafluorophen-1-yl, dimethylcyclopentagenyl-Ti-bis-2,6-difluorophen-1-yl, dicyclopentaje Le -Ti-2,6-difluoro-3- (pyrr-1-yl) - titanocene derivatives such as 1-yl;

2-Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylamino Propiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone Α-aminoalkylphenone compounds such as
1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3- Yl] -1- (O-acetyloxime).

Among these, an oxime ester compound is preferable from the viewpoint of sensitivity and surface properties.
Oxime ester compounds have a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals in the structure, so they are highly sensitive in small amounts and stable against thermal reactions. Therefore, it is possible to design a photosensitive resin composition with high sensitivity in a small amount. In particular, an oxime ester-based compound having a carbazole ring which may have a substituent is preferable from the viewpoint of light absorption with respect to i-line (365 nm) of an exposure light source.

  As an oxime ester type compound, the compound represented by the following general formula (I-1) is mentioned, for example.

In the formula (I-1), R ^21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
R ^21b represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring.
R ^22a represents an alkanoyl group which may have a substituent, or an aryloyl group which may have a substituent.

The number of carbon atoms of the alkyl group in R ^21a is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity to exposure, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, more preferably 5 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a cyclopentylethyl group, and a propyl group.
Examples of the substituent that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and 4- (2-methoxy-1-methyl) ethoxy-2-methylphenyl. Group or N-acetyl-N-acetoxyamino group, and the like, and from the viewpoint of ease of synthesis, it is preferably unsubstituted.

Examples of the aromatic ring group for R ^21a include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the photosensitive coloring composition. Further, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, further preferably 12 or less, and particularly preferably 8 or less.

Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, and a furyl group. Among these, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable from the viewpoint of developability.
Examples of the substituent that the aromatic ring group may have include a hydroxyl group, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, a carboxyl group, a halogen atom, and an amino group. , An amide group, an alkyl group, and the like. From the viewpoint of developability, a hydroxyl group and a carboxyl group are preferable, and a carboxyl group is more preferable. Examples of the substituent in the alkyl group which may have a substituent and the alkoxy group which may have a substituent include a hydroxyl group, an alkoxy group and a halogen atom.
Among these, from the viewpoint of developability, R ^21a is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and even more preferably a methyl group. .

R ^21b is an arbitrary substituent containing an aromatic ring or a heteroaromatic ring. From the viewpoints of solubility in a solvent and sensitivity to exposure, R ^21b has an optionally substituted carbazolyl group or substituent. Preferred examples include a thioxanthonyl group which may be substituted or a diphenyl sulfide group which may have a substituent, and a group obtained by linking these groups and a carbonyl group. Among these, from the viewpoint of light absorption with respect to i-line (365 nm) of the exposure light source, a carbazolyl group which may have a substituent, or a carbazolyl group which may have a substituent and a carbonyl group are linked. Groups are preferred.

The number of carbon atoms of the alkanoyl group in R ^22a is not particularly limited, but is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, more preferably, from the viewpoint of solubility in a solvent or sensitivity. 10 or less, more preferably 5 or less. Specific examples of the alkanoyl group include an acetyl group, an ethyloyl group, a propanoyl group, and a butanoyl group.
Examples of the substituent that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, and an amide group. From the viewpoint of ease of synthesis, the substituent may be unsubstituted. Is preferred.

The number of carbon atoms of the aryloyl group in R ^22a is not particularly limited, but is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, more preferably from the viewpoint of solubility in a solvent or sensitivity. 10 or less. Specific examples of the aryloyl group include a benzoyl group and a naphthoyl group.
Examples of the substituent that the aryloyl group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and an alkyl group. From the viewpoint of ease of synthesis, it is preferably unsubstituted. .

  Among the compounds represented by the general formula (I-1), the compound is represented by the following general formula (I-2) or (I-3) from the viewpoint of light absorption with respect to i-line (365 nm) of the exposure light source. Compounds.

In said formula (I-2) or (I-3), R ^<21a> and R ^<22a> are synonymous with the said general formula (I-1).
R ^23a represents an alkyl group which may have a substituent.
R ^24a represents an alkyl group that may have a substituent, an aryloyl group that may have a substituent, a heteroaryloyl group that may have a substituent, or a nitro group.
The benzene ring constituting the carbazole ring may be further condensed with an aromatic ring to form a polycyclic aromatic ring.

The number of carbon atoms of the alkyl group in R ^23a is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, from the viewpoint of solubility in a solvent. Preferably it is 5 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a cyclohexyl group.
Examples of the substituent that the alkyl group may have include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, or a nitro group. From the viewpoint of ease of synthesis, there is no substitution. It is preferable that

The carbon number of the aryloyl group in R ^23a is not particularly limited, but is usually 7 or more, preferably 8 or more, more preferably 9 or more, and usually 20 or less, preferably 15 or less, from the viewpoint of solubility in a solvent. Preferably it is 10 or less, More preferably, it is 9 or less. Specific examples of the aryloyl group include a benzoyl group and a naphthoyl group.
Examples of the substituent that the aryloyl group may have include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, or a nitro group. From the viewpoint of ease of synthesis, an ethyl group It is preferable that

The carbon number of the heteroaryloyl group in R ^23a is not particularly limited, but is usually 7 or more, preferably 8 or more, more preferably 9 or more, and usually 20 or less, preferably 15 or less, from the viewpoint of solubility in a solvent. More preferably, it is 10 or less, More preferably, it is 9 or less. Specific examples of the heteroaryl group include a fluorobenzoyl group, a chlorobenzoyl group, a bromobenzoyl group, a fluoronaphthoyl group, a chloronaphthoyl group, and a bromonaphthoyl group.
Examples of the substituent that the heteroaryloyl group may have include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, or a nitro group. Substitution is preferred.
Among these, R ^23a is preferably an alkyl group, more preferably an ethyl group, from the viewpoint of solubility in a solvent and ease of synthesis.

  The benzene ring constituting the carbazole ring may be further condensed with an aromatic ring to form a polycyclic aromatic ring.

  As commercially available products of such oxime ester compounds, OXE-02, OXE-03 manufactured by BASF, TR-PBG-304, TR-PBG-314 manufactured by Changzhou Power Electronics, or N-1919 manufactured by ADEKA, NCI-930, NCI-831, etc.

  Specific examples of the oxime ester-based compound include compounds exemplified below, but the oxime ester-based compound is not limited to these compounds.

  These photopolymerization initiators may be used alone or in combination of two or more.

  In the colored resin composition of the present invention, the content ratio of the photopolymerization initiator (F) is not particularly limited, but is preferably 0% by mass or more, and 0.3% by mass or more based on the total solid content of the colored resin composition. More preferably, 0.4% by mass or more is further preferable, 0.5% by mass or more is particularly preferable, 10% by mass or less is preferable, 7% by mass or less is more preferable, 5% by mass or less is further preferable, and 3% by mass. % Or less is more preferable, and 2% by mass or less is particularly preferable. By setting it to the lower limit value or more, the linearity tends to be improved, and by setting the upper limit value or less, the solubility is improved, particularly, the residue tends to be suppressed.

[1-7] Other solid content The colored resin composition of the present invention may further contain a solid content other than the above components as required. Examples of such components include a dispersion aid and a surfactant.

[1-7-1] Dispersion aid When the colored resin composition of the present invention contains a pigment, it contains a pigment derivative or the like as a dispersion aid in order to improve the dispersibility of the pigment and the dispersion stability. Also good. As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, isoindoline, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolo Derivatives such as pyrrole and dioxazine pigments may be mentioned. Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment skeleton or alkyl groups, aryl groups, and complex groups. Examples thereof include those bonded via a ring group and the like, preferably a sulfonamide group and a quaternary salt thereof, and a sulfonic acid group, and more preferably a sulfonic acid group. In addition, a plurality of these substituents may be substituted on one pigment skeleton, or a mixture of compounds having different numbers of substitutions. Specific examples of pigment derivatives include azo pigment sulfonic acid derivatives, phthalocyanine pigment sulfonic acid derivatives, quinophthalone pigment sulfonic acid derivatives, isoindoline pigment sulfonic acid derivatives, anthraquinone pigment sulfonic acid derivatives, quinacridone pigment sulfonic acid derivatives, Examples thereof include sulfonic acid derivatives of diketopyrrolopyrrole pigments and sulfonic acid derivatives of dioxazine pigments.

[1-7-2] Surfactant A variety of surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used as surfactants, which may adversely affect various properties. It is preferable to use a nonionic surfactant from the viewpoint of low. The content ratio of the surfactant is usually 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0%, based on the total solid content of the colored resin composition. The range of 1% by mass or more, usually 10% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less, and most preferably 0.3% by mass or less is used.

[2] Preparation of Colored Resin Composition Next, a method for preparing the colored resin composition according to the present invention (hereinafter sometimes referred to as a resist) will be described.

  When preparing a pigment containing a pigment as the colorant, first, a predetermined amount of each of the pigment, the solvent and the dispersant is weighed, and in the dispersion treatment step, the pigment containing pigment is dispersed to prepare a pigment dispersion. In this dispersion treatment step, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used. By performing this dispersion treatment, the coloring material is made fine particles, so that the coating characteristics of the colored resin composition are improved, and the transmittance of the pixels in the color filter substrate of the product is improved.

When dispersing the pigment, as described above, it is preferable to use a dispersion aid or a dispersion resin in combination as appropriate.
When the dispersion treatment is performed using a sand grinder, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several mm. The temperature during the dispersion treatment is usually set to 0 ° C. or higher, preferably room temperature or higher, and usually 100 ° C. or lower, preferably 80 ° C. or lower. The dispersion time varies depending on the composition of the pigment dispersion, the size of the sand grinder apparatus, and the like, and therefore needs to be adjusted appropriately.

  The pigment dispersion obtained by the dispersion treatment is mixed with a solvent, a binder resin, a photopolymerization initiator, and in some cases, components other than those described above to obtain a uniform dispersion solution. In each of the dispersion treatment step and the mixing step, fine dust may be mixed. Therefore, the obtained pigment dispersion is preferably filtered with a filter or the like.

[3] Production of Color Filter Substrate Next, the color filter according to the present invention will be described.
The color filter which concerns on this invention has a pixel formed using the above-mentioned colored resin composition.

[3-1] Transparent substrate (support)
The transparent substrate of the color filter is not particularly limited as long as it is transparent and has an appropriate strength. Examples of materials include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, polysulfone thermoplastic resin sheets, epoxy resins, unsaturated polyester resins, and poly (meth) acrylic. Examples thereof include thermosetting resin sheets such as a resin, and various glasses. Among these, glass or heat resistant resin is preferable from the viewpoint of heat resistance.

  For transparent substrates and black matrix forming substrates, to improve surface properties such as adhesion, corona discharge treatment, ozone treatment, thin film formation treatment of various resins such as silane coupling agents and urethane resins, as necessary May be performed. The thickness of the transparent substrate is usually 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, preferably 7 mm or less. Moreover, when performing the thin film formation process of various resin, the film thickness is 0.01 micrometer or more normally, Preferably it is 0.05 micrometer or more, and is 10 micrometers or less normally, Preferably it is the range of 5 micrometers or less.

[3-2] Black Matrix A color filter according to the present invention can be manufactured by providing a black matrix on the above-described transparent substrate and further forming pixel images of red, green, and blue normally. The colored resin composition is preferably used as a coating solution for forming a green pixel (resist pattern) among red, green and blue pixels (hereinafter sometimes abbreviated as “green resist”). Using the green resist, on a resin black matrix forming surface formed on a transparent substrate, or on a metal black matrix forming surface formed using a chromium compound or other light shielding metal material, coating, heat drying, image exposure, Each process of development and thermosetting is performed to form a pixel image.

The black matrix is formed on a transparent substrate using a light shielding metal thin film or a colored resin composition for black matrix. As the light-shielding metal material, chromium compounds such as metal chromium, chromium oxide, and chromium nitride, nickel and tungsten alloys, and the like may be used, and these may be laminated in a plurality of layers.
These metal light shielding films are generally formed by a sputtering method, and after forming a desired pattern in a film shape with a positive photoresist, ceric ammonium nitrate, perchloric acid and / or nitric acid are added to chromium. Other materials are etched using an etchant according to the material, and finally a positive photoresist is stripped with a dedicated stripper to form a black matrix. be able to.

  In this case, first, a thin film of the metal or metal / metal oxide is formed on the transparent substrate by vapor deposition or sputtering. Next, after forming a coating film of the colored resin composition on the thin film, the coating film is exposed and developed using a photomask having a repeated pattern such as stripes, mosaics, and triangles to form a resist image. Thereafter, this coating film can be etched to form a black matrix.

  When using the photosensitive coloring resin composition for black matrix, a black matrix is formed using the coloring resin composition containing a black coloring agent. For example, black color material such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black or the like, or red, green, blue or the like appropriately selected from inorganic or organic pigments and dyes A black matrix can be formed in the same manner as described below for forming a red, green, and blue pixel image using a colored resin composition containing a black color material by mixing.

[3-3] Formation of Pixels The pixel formation method varies depending on the type of the colored resin composition to be used. Here, a case where a photopolymerizable composition is used as the colored resin composition will be described as an example.
On a transparent substrate provided with a black matrix, a colored resin composition of one of red, green, and blue is applied and dried, and then a photomask is overlaid on the coating film, and image exposure is performed through this photomask. A pixel image is formed by development and, if necessary, thermosetting or photocuring. A color filter image can be formed by performing this operation for each of the three colored resin compositions of red, green, and blue.

  The color resin composition for color filters can be applied by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. Above all, according to the die coating method, the amount of coating solution used is greatly reduced, there is no influence of mist adhering when using the spin coating method, and the generation of foreign matter is further suppressed. It is preferable from a viewpoint.

  If the thickness of the coating film is too large, pattern development becomes difficult and gap adjustment in the liquid crystal cell forming process may be difficult. On the other hand, if it is too small, it is difficult to increase the pigment concentration. Color expression may be impossible. The thickness of the coating film is usually 0.2 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more, and usually 20 μm or less, preferably 10 μm or less, more preferably 5 μm as the film thickness after drying. The range is as follows.

[3-4] Drying of Coating Film The coating film after the colored resin composition is applied to the substrate is preferably dried by a drying method using a hot plate, IR oven, or convection oven. Usually, after preliminary drying, it is heated again and dried. The conditions for the preliminary drying can be appropriately selected according to the type of the solvent component, the performance of the dryer to be used, and the like. The drying temperature and drying time are selected according to the type of the solvent component, the performance of the dryer used, and the like. Specifically, the drying temperature is usually 40 ° C. or higher, preferably 50 ° C. or higher, and usually 80 The drying time is usually 15 seconds or longer, preferably 30 seconds or longer, and usually 5 minutes or shorter, preferably 3 minutes or shorter.

  The temperature condition for reheat drying is preferably higher than the pre-drying temperature. Specifically, it is usually 50 ° C. or higher, preferably 70 ° C. or higher, and usually 200 ° C. or lower, preferably 160 ° C. or lower, particularly preferably 130 ° C. It is the range below ℃. Moreover, although it depends on the heating temperature, the drying time is usually 10 seconds or more, preferably 15 seconds or more, and usually 10 minutes or less, preferably 5 minutes. The higher the drying temperature, the better the adhesion to the transparent substrate. However, when the drying temperature is too high, the binder resin is decomposed, and thermal polymerization may be induced to cause development failure. In addition, as a drying process of this coating film, you may use the reduced pressure drying method which dries in a reduced pressure chamber, without raising temperature.

[3-5] Exposure Step Image exposure is performed by superimposing a negative matrix pattern on the coating film of the colored resin composition and irradiating an ultraviolet light source or a visible light source through this mask pattern. At this time, if necessary, exposure may be performed after an oxygen blocking layer such as a polyvinyl alcohol layer is formed on the photopolymerizable layer in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen. The light source used for said image exposure is not specifically limited. Examples of the light source include a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, and a fluorescent lamp, an argon ion laser, a YAG laser, Examples include an excimer laser, a nitrogen laser, a helium cadmium laser, and a laser light source such as a semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

[3-6] Development Step The color filter according to the present invention is an organic solvent or surfactant after image exposure with the above-mentioned light source to the coating film using the colored resin composition according to the present invention. By carrying out development using an aqueous solution containing an alkaline compound and an alkaline compound, an image can be formed on a substrate for production. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

  Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethylamine Mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Machine alkaline compounds. These alkaline compounds may be a mixture of two or more.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters, and amphoteric surfactants such as alkylbetaines and amino acids.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent can be used alone or in combination with an aqueous solution.
There are no particular restrictions on the conditions of the development processing, but the development temperature is usually 10 ° C. or higher, especially 15 ° C. or higher, more preferably 20 ° C. or higher, and usually 50 ° C. or lower, especially 45 ° C. or lower, more preferably 40 ° C. or lower. Is preferred. The development method can be any method such as immersion development, spray development, brush development, and ultrasonic development.

[3-7] Thermosetting treatment The color filter after development is subjected to thermosetting treatment. In this case, the thermosetting treatment conditions are such that the temperature is usually 100 ° C. or higher, preferably 150 ° C. or higher, and usually 280 ° C. or lower, preferably 250 ° C. or lower. Selected by range. Through these series of steps, the patterning image formation for one color is completed. This process is sequentially repeated to pattern black, red, green, and blue to form a color filter. Note that the order of patterning the four colors is not limited to the order described above.

[3-8] Formation of Transparent Electrode The color filter according to the present invention forms a transparent electrode such as ITO on an image as it is, and is used as a part of a component such as a color display or a liquid crystal display device. However, in order to improve surface smoothness and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed.

[4] Image display device (panel)
Next, the image display apparatus of the present invention will be described. The image display device of the present invention has the color filter described above. Hereinafter, a liquid crystal display device and an organic EL display device will be described in detail as the image display device.

[4-1] Liquid Crystal Display Device A method for manufacturing a liquid crystal display device according to the present invention will be described. The liquid crystal display device according to the present invention is generally formed by forming an alignment film on the color filter according to the present invention, spraying spacers on the alignment film, and then bonding to a counter substrate to form a liquid crystal cell. The liquid crystal is injected into the liquid crystal cell and connected to the counter electrode to complete. The alignment film is preferably a resin film such as polyimide. For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to form a surface state in which the tilt of the liquid crystal can be adjusted.

  As the spacer, a spacer having a size corresponding to a gap (gap) with the counter substrate is used, and a spacer of 2 to 8 μm is usually preferable. A photo spacer (PS) of a transparent resin film can be formed on the color filter substrate by a photolithography method, and this can be used instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 μm or more and 8 μm or less. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of vacuum in the liquid crystal cell is usually in the range of 1 × 10 ⁻² Pa or more, preferably 1 × 10 ⁻³ Pa or more, and usually 1 × 10 ⁻⁷ Pa or less, preferably 1 × 10 ⁻⁶ Pa or less. . The liquid crystal cell is preferably heated during decompression, and the heating temperature is usually 30 ° C. or higher, preferably 50 ° C. or higher, and usually 100 ° C. or lower, preferably 90 ° C. or lower.

The warming holding at the time of depressurization is usually in the range of 10 minutes or more and 60 minutes or less, and then immersed in the liquid crystal. In the liquid crystal cell into which liquid crystal is injected, a liquid crystal display device (panel) is completed by sealing the liquid crystal injection port by curing the UV curable resin.
The type of liquid crystal is not particularly limited, and may be any of conventionally known liquid crystals such as aromatic, aliphatic, and polycyclic compounds, and may be any of lyotropic liquid crystals, thermotropic liquid crystals, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of them may be used.

[4-2] Organic EL Display Device When producing an organic EL display device having the color filter of the present invention, for example, as shown in FIG. 1, a pixel 20 is formed on a transparent support substrate 10 by the colored resin composition of the present invention. A multicolor organic EL element is produced by laminating the organic light-emitting body 500 on the blue color filter formed with the organic protective layer 30 and the inorganic oxide film 40 therebetween.

  As a method for laminating the organic light emitter 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. The organic EL element 100 manufactured as described above can be applied to both a passive drive type organic EL display device and an active drive type organic EL display device.

  EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.

<Green pigment>
C. I. Pigment Green 58 (manufactured by DIC, FASTOGEN Green A350)
<Yellow pigment>
C. I. Pigment Yellow 138

<Dispersant A>
A methacrylic acid AB block copolymer comprising an A block having a nitrogen atom-containing functional group and a B block having a solvophilic group. The A block has a repeating unit represented by the following formula (a1), and the B block has a repeating unit represented by the following formula (b1). The content ratios of the repeating unit represented by the following formula (a1) and the repeating unit represented by the following formula (b1) in all repeating units are 13 mol% and 87 mol%, respectively. The amine value is 70 mgKOH / g, the acid value is 0 mgKOH / g, and the weight average molecular weight Mw is 8000.

<Dispersant B>
A methacrylic acid AB block copolymer comprising an A block having a nitrogen atom-containing functional group and a B block having a solvophilic group. The A block has a repeating unit represented by the following formula (a1), and the B block has a repeating unit represented by the following formulas (b1) and (b2). The content ratio of the repeating unit represented by the following formula (a1), the repeating unit represented by the following formula (b1), and the repeating unit represented by the following formula (b2) in all repeating units is 25 mol%. 64 mol% and 11 mol%. The amine value is 120 mgKOH / g, the acid value is 0 mgKOH / g, and the weight average molecular weight Mw is 8000.

<Dispersant C: Dispersant “BYK-LPN6919” manufactured by Big Chemie>
A methacrylic acid AB block copolymer comprising an A block having a nitrogen atom-containing functional group and a B block having a solvophilic group. The A block has a repeating unit represented by the following formula (a1), and the B block has a repeating unit represented by the following formulas (b1) to (b5). The content ratio of the repeating unit represented by the following formula (a1) and the repeating units represented by (b1) to (b5) in all repeating units is 33 mol%, 26 mol%, 15 mol%, 13 Mol%, 9 mol% and 4 mol%. The amine value is 120 mgKOH / g, the acid value is 0 mgKOH / g, and the weight average molecular weight is Mw8000.

<Resin A>
Prepare a separable flask with a cooling tube as a reaction vessel, charge 400 parts by mass of propylene glycol monomethyl ether acetate, purge with nitrogen, and heat in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. did.

  Meanwhile, 30 parts by mass of dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, 60 parts by mass of methacrylic acid, 110 parts by mass of cyclohexyl methacrylate, t-butylperoxy-2-ethyl in the monomer tank Charge 5.2 parts by weight of hexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate, and 5.2 parts by weight of n-dodecyl mercaptan and 27 parts by weight of propylene glycol monomethyl ether acetate in a chain transfer agent tank After stabilizing at 90 ° C., dropping was started from the monomer tank and the chain transfer agent tank to initiate polymerization. While maintaining the temperature at 90 ° C., dropping was carried out over 135 minutes each, and 60 minutes after the dropping was finished, the temperature was raised and the reaction vessel was brought to 110 ° C.

After maintaining at 110 ° C. for 3 hours, a gas introduction tube was attached to the separable flask and bubbling of oxygen / nitrogen = 5/95 (v / v) mixed gas was started. Next, 39.6 parts by mass of glycidyl methacrylate, 0.4 parts by mass of 2,2′-methylenebis (4-methyl-6-tert-butylphenol), and 0.8 parts by mass of triethylamine were charged into the reaction vessel and left at 110 ° C. For 9 hours.
After cooling to room temperature, a resin A having a polystyrene-equivalent weight average molecular weight Mw measured by GPC of 8000 and an acid value of 101 mgKOH / g was obtained.

<Resin B>
145 parts by mass of propylene glycol monomethyl ether acetate was stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. 10 parts by mass of styrene, 85 parts by mass of glycidyl methacrylate, and 66 parts by mass of monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise thereto, and the mixture was further stirred at 120 ° C. for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 52 parts by mass of methacrylic acid, and the reaction was continued at 120 ° C. for 6 hours. Then, 60 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added and reacted at 120 ° C. for 3.5 hours. The weight average molecular weight Mw in terms of polystyrene measured by GPC of the resin B thus obtained was about 8000, and the acid value was 80 mgKOH / g.

<Photopolymerizable monomer>
Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (A-9550, manufactured by Shin-Nakamura Chemical Co., Ltd.)

<Photopolymerization initiator>
Oxime ester-based compound having the following chemical structure (methyl 4-acetoxyimino-5- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -5-oxopentanoate)

<Chain transfer agent>
Pentaerythritol tetra (3-mercaptopropionate) (manufactured by Sakai Chemical Co., Ltd.)

<Surfactant>
Megafuck F-559 (manufactured by DIC)

<Preparation of green pigment dispersions A to C>
13.8 parts by mass of a green pigment, 2.3 parts by mass of various dispersants listed in Table 1 as a dispersant, 3.9 parts by mass of resin A in terms of solids, and propylene glycol as a solvent Fill a stainless steel container with 80 parts by mass of monomethyl ether acetate (including a dispersant and a solvent contained in the resin) and 225 parts by mass of zirconia beads having a diameter of 0.5 mm, and disperse in a paint shaker for 6 hours. -C was prepared. About the obtained green pigment dispersions A to C, before and after storage at 35 ° C. for 3 days, the viscosity at 23.0 ± 1.0 ° C. using an E-type viscometer “RE-80L” manufactured by Toki Sangyo Co., Ltd. Was measured. The results are shown in Table 1.

<Preparation of yellow pigment dispersion>
11.9 parts by mass of a yellow pigment, 4.1 parts by mass of the dispersant C in terms of solid content, 6.0 parts by mass of resin A in terms of solid content, and 78 parts by mass of propylene glycol monomethyl ether acetate as a solvent (dispersion) 225 parts by weight of zirconia beads having a diameter of 0.5 mm were filled in a stainless steel container and dispersed in a paint shaker for 6 hours to prepare a yellow pigment dispersion.

<Preparation of colored resin composition>
(Examples 1 and 2 and Comparative Examples 1 to 3)
Each colored resin composition was prepared by mixing each pigment dispersion and other components in the amounts shown in Table 2. In addition, the compounding quantity of binder resin of Table 2 is a solid content conversion value, and the solvent quantity contained in binder resin is also contained in the compounding quantity of a solvent.

<Measurement of voltage holding ratio>
An electrode substrate A in which an ITO film is formed on the entire surface of one side of a 2.5 cm square alkali-free glass substrate ("AN-100" manufactured by Asahi Glass Co., Ltd.), and a 2 mm wide takeout at the center of one side of the 2.5 cm square glass substrate An electrode substrate B on which a 1 cm square ITO film with electrodes connected was formed.

The colored resin compositions of Examples 1 and 2 and Comparative Examples 1 to 3 were applied on the electrode substrate A by spin coating, and dried on a hot plate at 80 ° C. for 3 minutes. The coating conditions were adjusted so that the film thickness of the fired coating film was 2.5 μm.
Next, the entire surface of the coating film was exposed at 60 mJ / cm ² with a 2 kW high-pressure mercury lamp. Then, spray development was performed for 50 seconds at a pressure of 0.1 MPa with a 0.04 mass% aqueous potassium hydroxide solution at 23 ° C. Next, spray water washing treatment was performed for 10 seconds at a water pressure of 0.1 MPa, and then baking was performed at 230 ° C. for 30 minutes in a hot air circulating furnace.

  Next, on the outer periphery of the electrode substrate B, a dispenser is used to apply an epoxy resin-based sealant containing silica beads having a diameter of 5 μm, and then the surface of the electrode substrate A on which the colored resin composition is applied is Were placed facing each other so as to shift by 3 mm, and heated in a hot air circulating furnace at 180 ° C. for 2 hours while being pressure-bonded.

  A liquid crystal ("MLC-6846-000" manufactured by Merck Japan Co., Ltd.) was injected into the empty cell obtained as described above, the periphery was sealed with a UV curable sealant, and a liquid crystal cell for measuring voltage holding ratio was obtained. completed.

  Next, the liquid crystal cell was heated at 105 ° C. for 2.5 hours in a hot air circulating furnace. Thereafter, a pulse voltage was applied between the electrode substrates A and B under conditions of an applied voltage of 5 V and a pulse frequency of 60 Hz and 2 Hz, and the voltage holding ratio was measured. Table 3 shows the measurement results of the voltage holding ratio of each colored resin composition.

<Evaluation of color characteristics>
Each colored resin composition was applied on a 50 mm square, 0.7 mm thick glass substrate (“AN-100” manufactured by Asahi Glass Co., Ltd.) using a spin coater, and then dried at 80 ° C. for 3 minutes. The rotational speed was adjusted so that the film thickness after the thermosetting treatment was 2.5 μm.
Subsequently, the whole surface exposure process was performed with the exposure amount of 60 mJ / cm < ² > with the 2kW high pressure mercury lamp. Thereafter, spray development was carried out with a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a pressure of 0.1 MPa for 50 seconds. Subsequently, the spray water washing process was performed for 10 second at 0.1 MPa pressure, and the thermosetting process for 30 minutes was performed at the temperature of 230 degreeC after that, and the application board | substrate was created.
With respect to the coated substrate thus obtained, a transmission spectrum was measured with a spectrophotometer U-3310 manufactured by Hitachi, Ltd. Table 4 shows the chromaticity (x, y) and luminance (Y) calculated with the C light source.

<Evaluation of dissolution time and linearity>
Each colored resin composition was spin-coated on a glass substrate on which chromium was deposited, and prebaked for 3 minutes on a hot plate at 80 ° C. Regarding coating, the number of revolutions was adjusted so that the film thickness after thermosetting for 30 minutes was 2.5 μm at a temperature of 230 ° C.
Next, after exposure at 60 mJ / cm ² through a mask having a linear opening with a width of 50 μm and a length of 3 mm using a 2 kW high-pressure mercury lamp, a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. Spray development was performed at a pressure of 0.25 MPa. The development time was set to twice the dissolution time of each colored resin composition measured in advance. In addition, the time which the colored resin composition of the unexposed part melt | dissolved completely in the developing solution and the board | substrate was exposed was made into the dissolution time of the colored resin composition. After development, the substrate was rinsed with sufficient water and then dried with clean air.

The obtained five linear patterns were observed at a magnification of 10 using an optical microscope, the number of edges of the pattern was counted, and evaluated according to the following criteria. The dissolution time and linearity results are shown in Table 5.
○: Number of hooks from 0 to 5 Δ: Number of hooks from 6 to 10

From Table 3, it is clear that the colored resin composition of the present invention has a high liquid crystal voltage holding ratio.
In Examples 1 and 2, by including Dispersant A or Dispersant B having 50% by mole or more of the repeating unit represented by the general formula (I), the affinity with the liquid crystal molecules is reduced, and the pigment And the steric repulsion of the dispersant is suppressed, and the adsorption of the adsorption group in the dispersant to the pigment is promoted. For this reason, it is considered that the free dispersant is prevented from being eluted into the liquid crystal, and the voltage holding ratio of the liquid crystal, particularly the voltage holding ratio under a low frequency condition is improved. In addition, it includes the resin B having the repeating unit represented by the general formula (i), and the carboxyl group is bonded to a highly fluid side chain, so that intramolecular association due to hydrogen bonding between the carboxyl groups is less likely to occur. The ethylenic double bond is likely to face the outside of the molecule, so that the curability is increased and the voltage holding ratio is increased.

  On the other hand, Comparative Example 1 does not contain a dispersant having 50% by mole or more of the repeating unit represented by the general formula (I), so that a large amount of the free dispersant is eluted into the liquid crystal, thereby maintaining the voltage. It is considered that the voltage holding ratio in the low frequency condition is low.

  In Comparative Examples 2 and 3, the resin having the repeating unit represented by the general formula (i) is not included, and the resin A having the repeating unit derived from (meth) acrylic acid is included, but the resin is derived from (meth) acrylic acid. Since the carboxyl group is in the vicinity of the main chain, the fluidity is low, the intramolecular association due to the hydrogen bond between the carboxyl groups is likely to occur, and the ethylenic double bond tends to face the inside of the molecule, resulting in low curability. It is considered that the voltage holding ratio has decreased.

Moreover, from Table 4, the colored resin composition of the present invention has high luminance.
In Examples 1 and 2, thermosetting is achieved by including Dispersant A or Dispersant B having 50 mol% or more of the repeating unit represented by Formula (I) having a small number of carbons in the side chain and high heat resistance. It is considered that thermal decomposition due to the treatment is difficult to occur, and coloring and luminance reduction accompanying thermal decomposition are suppressed. On the other hand, Comparative Example 1 does not contain a dispersant having 50% by mole or more of the repeating unit represented by the general formula (I), and thus has low heat resistance, is thermally decomposed by thermosetting treatment, and decreases brightness by coloring. It is thought that.

Furthermore, from Table 5, the colored resin compositions of Examples 1 and 2 have a short dissolution time of 30 seconds or less, whereas the colored resin compositions of Comparative Examples 2 and 3 exceed 40 seconds and are not suitable for producing a color filter. I understood it. In addition, it was found that Examples 1 and 2 had fewer linear patterns compared to Comparative Examples 2 and 3, and a pattern having good linearity was obtained.
Examples 1 and 2 contain a resin B having a repeating unit represented by the above general formula (i) having a structure in which a carboxyl group is added to a highly fluid side chain as a binder resin, so that the carboxyl group and development can be performed. It is considered that the contact efficiency with the liquid is high and the dissolution time is shortened. On the other hand, Comparative Example 1 includes a resin A obtained by copolymerizing (meth) acrylic acid and other components as a binder resin, so that the contact efficiency between the carboxyl group derived from (meth) acrylic acid and the developer is improved. The dissolution time is considered to be low.

DESCRIPTION OF SYMBOLS 100 Organic EL element 10 Transparent support substrate 20 Pixel 30 Organic protective layer 40 Inorganic oxide film 50 Transparent anode

Claims (4)

A colored resin composition comprising (A) a colorant, (B) a dispersant, (C) a solvent, (D) a binder resin, (E) a photopolymerizable monomer, and (F) a photopolymerization initiator,
The (B) dispersant includes a dispersant (b) having 50 mol% or more of a repeating unit represented by the following general formula (I):
The colored resin composition, wherein the binder resin (D) includes an alkali-soluble resin (d) having a repeating unit represented by the following general formula (i).

(In formula (I), R ¹ represents a hydrogen atom or a methyl group. R ² represents an alkyl group having 3 or less carbon atoms which may have a substituent.)

(In formula (i), R ^d1 represents a hydrogen atom or a methyl group.
R ^d2 represents a trivalent hydrocarbon group which may have a substituent.
R ^d3 represents a hydrogen atom or a methyl group.
R ^d4 represents a divalent hydrocarbon group which may have a substituent. )   The colored resin composition according to claim 1, wherein the colorant (A) contains a halogenated zinc phthalocyanine pigment.   The color filter which has a pixel created using the colored resin composition of Claim 1 or 2.   An image display device comprising the color filter according to claim 3.

Images